Computational analysis reveals cyclopropenyl cation-like π aromaticity in zinc-group boron clusters M3B3+, highlighting an unusual aromaticity reversal upon electronic excitation.
Planar boron clusters often display π-bonding patterns analogous to those found in aromatic hydrocarbons, making them intriguing inorganic counterparts of classical hydrocarbon systems. Herein, we report zinc-group element-stabilized boron analogues of the cyclopropenyl cation (C3H3+), formulated as M3B3+ (M = Zn, Cd, and Hg). Global minimum searches reveal that these clusters adopt highly symmetric D3h structures with a 1A1′ electronic ground state and exhibit pronounced dynamic stability. Chemical bonding analyses demonstrate that M3B3+ reproduces the fundamental bonding motif of the cyclopropenyl cation, consisting of covalent M-B interactions and a three-center two-electron (3c–2e) π bond delocalized over the B3 core. The resulting π-electron system satisfies Hückel’s (4n + 2) rule, giving rise to π aromaticity, as supported by magnetic aromaticity indices. Notably, in M3B3+ (M = Zn and Cd), the vertical T1 excited states exhibit σ-antiaromaticity, highlighting an unusual aromaticity reversal upon electronic excitation.
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yin et al. (2026) studied this question.
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